Computationally Guided Design of a Readily Assembled Phosphite- Thioether Ligand for a Broad Range of Pd-Catalyzed Asymmetric Allylic Substitutions

A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson–Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures

Analytical and numerical analyses of the micromechanics of soft fibrous connective tissues

State of the art research and treatment of biological tissues require accurate and efficient methods for describing their mechanical properties. Indeed, micromechanics motivated approaches provide a systematic method for elevating relevant data from the microscopic level to the macroscopic one. In this work the mechanical responses of hyperelastic tissues with one and two families of collagen fibers are analyzed by application of a new variational estimate accounting for their histology and the behaviors of their constituents. The resulting, close form expressions, are used to determine the overall response of the wall of a healthy human coronary artery. To demonstrate the accuracy of the proposed method these predictions are compared with corresponding 3-D finite element simulations of a periodic unit cell of the tissue with two families of fibers. Throughout, the analytical predictions for the highly nonlinear and anisotropic tissue are in agreement with the numerical simulations

Relationship between Structure, Entropy and Diffusivity in Water and Water-like Liquids

Anomalous behaviour of the excess entropy ($S_e$) and the associated scaling relationship with diffusivity are compared in liquids with very different underlying interactions but similar water-like anomalies: water (SPC/E and TIP3P models), tetrahedral ionic melts (SiO$_2$ and BeF$_2$) and a fluid with core-softened, two-scale ramp (2SRP) interactions. We demonstrate the presence of an excess entropy anomaly in the two water models. Using length and energy scales appropriate for onset of anomalous behaviour, the density range of the excess entropy anomaly is shown to be much narrower in water than in ionic melts or the 2SRP fluid. While the reduced diffusivities ($D^*$) conform to the excess entropy scaling relation, $D^* =A\exp (\alpha S_e)$ for all the systems (Y. Rosenfeld, Phys. Rev. A {\bf 1977}, {\it 15}, 2545), the exponential scaling parameter, $\alpha$, shows a small isochore-dependence in the case of water. Replacing $S_e$ by pair correlation-based approximants accentuates the isochore-dependence of the diffusivity scaling. Isochores with similar diffusivity scaling parameters are shown to have the temperature dependence of the corresponding entropic contribution. The relationship between diffusivity, excess entropy and pair correlation approximants to the excess entropy are very similar in all the tetrahedral liquids.Comment: 24 pages, 4 figures, to be published in Journal of Physical Chemistry

Learning from Poverty: Why Business Schools Should Address Poverty, and How They Can Go About It.

In the past few years, business schools have begun to address poverty issues in their teaching, learning and curricula. While this is a positive development, the arguments for reconfiguring educational programs to address such matters remain undeveloped, with much of the impetus for such endeavors rooted in calls for social responsibility in the United Nations Millennium Development Goals, the Social Compact, the Principles for Responsible Management Education and benchmarks such as ISO 26000. This article seeks to clarify the pedagogical grounds for integrating poverty issues in management education by examining the intellectual and personal development benefits of doing so. By critically examining four modes of business involvement in poverty reduction, the article shows how such initiatives can be used as intellectual lenses through which to view the complex and often paradoxical interconnections between socioeconomic and environmental systems. It is thus concluded that a consideration of poverty issues is not a marginal matter, but is key to grasping the 21st century complexities of global business and management

Homogenization estimates for fiber-reinforced elastomers with periodic microstructures

This work presents a homogenization-based constitutive model for the mechanical behavior of elastomers reinforced with aligned cylindrical fibers subjected to finite deformations. The proposed model is derived by making use of the second-order homogenization method [Lopez-Pamies, O., Ponte Castañeda, P., 2006a. On the overall behavior, microstructure evolution, and macroscopic stability in reinforced rubbers at large deformations: I—theory. J. Mech. Phys. Solids 54, 807–830], which is based on suitably designed variational principles utilizing the idea of a “linear comparison composite.” Specific results are generated for the case when the matrix and fiber materials are characterized by generalized Neo-Hookean solids, and the distribution of fibers is periodic. In particular, model predictions are provided and analyzed for fiber-reinforced elastomers with Gent phases and square and hexagonal fiber distributions, subjected to a wide variety of three-dimensional loading conditions. It is found that for compressive loadings in the fiber direction, the derived constitutive model may lose strong ellipticity, indicating the possible development of macroscopic instabilities that may lead to kink band formation. The onset of shear band-type instabilities is also detected for certain in-plane modes of deformation. Furthermore, the subtle influence of the distribution, volume fraction, and stiffness of the fibers on the effective behavior and onset of macroscopic instabilities in these materials is investigated thoroughly